Dyestuff of the triphenyl methane series



Patented Nov. 10, 1931 UNITED STATES PATENT OFFICE? ms GROTOWSKY, on unnnl venn, GERMANY, AssIeivon To; GENERAL' ,ANIIJINE WORKS, INC., on NEW YORK, n. Y., A CORPORATION OF DELAWARE nYEs'rUrr on T m 'rnrri-rnnvn METHANE snnins No Drawing. Applieation filed April 15, 1929, Serial No. 355,439, and in Germany April 17, 1928.

The invention relates to new dyestuffs of the triphenyl methane" series. .e

I have found that byreacting with w or B-chloro ethyl benzene upon primary or sec- 8 ondary aromatic amines there are obtained new secondary or tertiary aromatic amines containing the group[C H .G H attached to the nitrogen ([0 11 being either an ethylene groupCI-I .CH or an ethylidene group CH .CH= These amines or the sulfonic acids thereof yield by condensation with aromatic aldehydes, ketones or-hydick and, if necessary, by subsequent oxidation new dyestuffs of the triphenyl methane 15 series.

For exampleby heating a mixture of '2 moles of monethyl aniline and 1111016 of ,8- chloro-ethyl benzene to about 100 C. there results ethyl ,B-phenyl-ethyl aniline corresponding to the formula which is an oilboiling'from 19s to 200 o. g at a pressure of 20mm. (mercury gauge). In quite an analogous way there is obtained from o-toluidine and a-chloroethyl benzene monoa-methylbenzyl o-toluidine Y which boils from 182 to pressure (mercury gauge) and melts at 38 to40 0.. 7

These and all the other aromatic amines V furic. acid and adding fuming sulfuric-acid 186? G. at 20 mm.'

containing about 65 percent of sulfur trioxide at about 30--50 C. The sulfonic acids thus obtained are partly resinous bodies, partly they represent well-defined crystalline compounds.

By condensing the amines sulfonatedor not sulfonated with aldehydes, such as benzaldehyde' and the substitution products thereof, or hydrols, such as tetra-methyl diamido .benzhydrol, there result leuco acids or l-euco bases which are readily oxidized to the corresponding dyestuffs. -The latter are di rectly produced by condensing the amines with ketones, such as Michlers ketone.

The new triphenyl methane dyestuffsin l particular if they are aciddyestutl's containing a sulfo group'-are distinguished by an excellent clarity of shade which isdifl'erent from the tint of the corresponding dyestufi's produced from benzylated aromatic amines, sucl)1 "as formyl violet (Colour Index No. 698 x The invention is illustrated by the following examples. The parts are by weight.

x pl .of ethyl a-methylbenzyl "aniline (boiling from 174: to 17 8 C; at 20 mm.pressure) are melted together with phosphorus oxychloride at about 90'to 95 C. After-decomposing the melt by water or sodium chloride solution there is obtained an a-methylbenzyl shade than benzyl violet (Colour Index No. 697).

on, our;

-Ewampte2 i parts of a-methylbenzyl o-toluidine sulfonic acid (obtained by sulfonating the aforesaid amine by means of fuming sulfuric acidcontaining about 65 percent of sulfur trio'xide 270 parts of Michlers ketone and 225 parts a violet which has a slightly more. reddish It isbelieved to correspond to the I formula: Y

ble formula at a temperature of 30-40 C.) are heated together with about 250 parts of water at a temperature of 100 0., until the aldehyde has disappeared. 145 parts of the resulting leuco acid are dissolved in 21 parts of sodium carbonate and 2500 parts of water and oxidized by means {of lead dioxide or sodium bichromate and sulfuric acid'in the known way. The dyestuff is precipitated-by-pourin the reaction mixture into sodium chloride solutiona-nd purified by dissolving it in hot water and cooling down the solution.

The dyestufi' thus aobtainedzhas the proba- It is, after drying, a 'viol'e't'powder which dyes wool from an acid bath more bluish shade than the corresponding dye'stuif from o-chloro benzaldehyde and 'ben'zyl o-toluidine. Moreover, the leuco compound of the new 'dyestuff is-m'uch more readily oxidized th'anfthat of "the 'dyestuif from benzyl ov iEma mph; 3

By substituting o chloro benzaldehyde in Example 2 by 190 parts of o-sulfo benzaldehyde a corresponding leuco acid is obtained. On oxidizing itin the same -vva asshown in Example 2 there results-adyestuif whichis fa violet .powder and dyes wool from :an, acid bath blue. 1t has the probable formula:

om om 508E NH-oHOsozH I it CH; d m I Ewample 4 p 1 100 parts of formaldehyde 'solution ('30 percent) arecondensed with'610 parts -of the sulfonic acid from ethyl ,B-phenylethyl aniline (obtained by sulfonating the said amine by means .of fuming sulfuric acid containing percent of sulfur trioxide at a temperature of '30 to 40 '612 parts of the resulting derivative .of vdiphenyl methane are heated together with 149 parts of .diethyl'aniline'and the twentyfold amount p i I claimi stuff.

of water at (3., cooled down to 40 C. and mixed with such an amount of sodium bi chromate as corresponds to 134: parts of chromium trioxide. There is obtained a dyestufi' which is a reddish violet powder and m which dyes WOOl from an acid bath considerablyrmore bluish and clearer shade than the corresponding d'yestufi from diphenyl methane derivative produced from formaldehyde-and ethyl benzyl=-aniline sulfonic acid and diethyl :anil-i-ne v(form yl violet, Colour Index No. 698 The new dyestufi' correspondsprobably to the formula:

h a Y r a =N-CH1-CH1OSOI (carom-O 'l O-N-om-cm-O-som tin, f. Q

1. Process which comprises condensing an aromatic amine containing a group [C H ]C -H attached to the nitrogen 80 with a compound of the group consisting of aromatic aldehydes, ketones and hydrols-and converting the leuco compound into-a-dyeamino with a compound =of-the group, consisting of aromatic aldehydes, ;ketones and :hydrols and converting the leuco compound into :a .dyestufi. I

4. Process which comprises reacting With- J fi-chloroethyl benzene upon a non-tertiary aromatic amine, condensing the phenylethylated amine with ean aromatic carbonyl compound and oxidizing the leuco compound to a 7115 '15, New dyestuffs of the 'triphenyl methane series corresponding to the general formula (wherein R R and R are phenyl radicals and X-rep-resentsfaisulfo group or an unsub- I stituted nuclear hydrogen atom) containing at least one amino vgroup substituted .a group [G IL]C H attachedgto the nitrogeneatom.

methane series corresponding to the general formula (wherein R R and R are phenyl radicals) containing a sulfo group and at least one amino group substituted by agroup [C H ]-C H attached to the nitrogen atom.

7. New acid dyestuffs of the triphenyl, methane series corresponding to the general formula I R; C R| R: V (wherein R R and R are phenyl radicals) containing a sulfo group and at least one amino group substituted by a phenyl ethyl group CI-I .CH G H, attached to the nitrogen atom.

8. A new acid dyestufi of the triphenyl methane series probably corresponding to the formula (OzHOaN which is in a dry state a reddish violet powder and dyes wool from an acid bath bluish violet shades.

In testimony whereof I have hereunto set my hand.

HANS GROTOWSKY. 

